JPH0251460B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antistatic resin composition that has permanent antistatic properties and excellent mechanical properties. Synthetic polymer materials are used in a wide range of fields due to their excellent properties, but they generally have high electrical resistivity and are easily charged, resulting in various problems caused by static electricity. Conventionally, in order to impart antistatic properties to synthetic polymer materials, there have been two methods: (1) incorporating water-absorbing compounds such as polyalkylene oxide and antistatic agents into polymers, and (2) adding surfactants to the surface. However, neither method achieves sufficient antistatic performance, and the antistatic property disappears when washed with water or the surface is wiped. There are problems such as the kneaded components bleed out onto the surface, resulting in a decrease in the quality of the material, and the antistatic properties deteriorate over time. Compared to these additive-type polymers, so-called polyether ester amide, in which polyamide and polyether are ester bonded via dicarboxylic acid, has excellent rubber elasticity and is also a polymer with good antistatic properties itself. Are known. However, polyetheresteramide is a rubber-like elastic body and has insufficient mechanical strength, so it has the disadvantage that it cannot be used as a structural material that requires rigidity and toughness. Moreover, polyetheresteramide can be used with other thermoplastic resins, such as polystyrene,
Styrene-acrylonitrile copolymer (SAN resin), polymethyl methacrylate, styrene-methyl methacrylate copolymer, acrylonitrile-butadiene-styrene terpolymer (ABS resin)
Resin compositions that do not have desirable mechanical properties may have poor compatibility with vinyl polymers such as, and even when mixed with these ordinary thermoplastic resins, delamination may occur or impact strength may be poor. can't get it. Therefore, although polyether ester amide has excellent antistatic properties, it has not yet been realized that this property can be utilized as an antistatic resin. On the other hand, polyglutarimide, which has recently been proposed as a new imide-based polymer with excellent heat resistance in Japanese Patent Application Laid-Open No. 52-63989, has a high heat distortion temperature, but has poor mechanical properties such as impact strength. Currently, its use as a molding material is limited due to its inferiority. The present inventors have conducted intensive studies on the modification of polyether ester ester amide with the aim of developing an antistatic resin that has permanent antistatic properties and excellent mechanical properties. Esteramide has specific compatibility with the above-mentioned polyglutarimide, and the inventors have discovered that the above object can be efficiently achieved by mixing the two in a specific ratio, and have thus arrived at the present invention. . That is, the present invention provides (A) (a) an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, (b) a poly(alkylene oxide) having a number average molecular weight of 200 to 6000; )
5 to 80% by weight of polyether ester amide composed of glycol and (c) dicarboxylic acid having 4 to 20 carbon atoms, and (B) 95 to 20% by weight of polyglitalimide.
The object of the present invention is to provide an antistatic resin composition formed by mixing % by weight. Polyetheresteramide is polystyrene,
It has poor compatibility with ordinary thermoplastic resins such as styrene-acrylonitrile copolymer (SAN resin), and even if they are mixed, only a resin composition with poor mechanical properties can be obtained. By mixing polyether ester amide and polyglutarimide, which have good compatibility and have the above composition, a resin composition with excellent mechanical properties and permanent antistatic properties can be obtained, and the effects of the present invention can be efficiently achieved. It is demonstrated. It is a constituent component of (A) polyether ester amide in the present invention. (a) Aminocarboxylic acids or lactams having 6 or more carbon atoms or 6 carbon atoms
As a salt of the above diamine and dicarboxylic acid, ω-
Aminocaproic acid, ω-aminoenanthate, ω-
Aminocaprylic acid, ω-aminopergonic acid, ω-
Aminocarboxylic acids such as aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid or lactams such as caprolactam, enantlactam, capryllactam and laurolactam and hexamethylenediamine-adipate, hexamethylenediamine-sebacate Salts of diamine dicarboxylic acids such as and hexamethylene diamine isophthalate are used, and hexamethylene diamine adipate is particularly preferably used. (A) Poly(alkylene oxide) glycol, which is a constituent component of polyether ester amide, includes polyethylene glycol, poly(1,2-
propylene oxide) glycol, poly(1,3
-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, and block or random copolymers of ethylene oxide and tetrahydrofuran. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties. The number average molecular weight of poly(alkylene oxide) glycol is used in the range of 200 to 6,000, especially 250 to 2,000. If the number average molecular weight is less than 200, the mechanical properties of the resulting polyether ester amide will be poor, and if the number average molecular weight is less than 6,000. If it exceeds it, the antistatic properties will be insufficient, which is not preferable. (A) The dicarboxylic acid (C) having 4 to 20 carbon atoms, which is a component of the polyether ester amide, is terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2, 7
-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and 3
- aromatic dicarboxylic acids such as sodium sulfoisophthalate, aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and succinic acid, oxalic acid, Examples include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and dodecanedicarboxylic acid. In particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid improve polymerizability, color tone, and It is preferably used from the viewpoint of physical properties. (A) There are no particular limitations on the polymerization method for polyether ester. For example, (a) (a) aminocarboxylic acid or lactam and (c) dicarboxylic acid are reacted in approximately equimolar ratios so that both terminals have carboxylic acid groups. (b) A method of reacting polyamide prepolymer with (b) poly(alkylene oxide) glycol under vacuum; (b) charging each compound of (a), (b), and (c) above into a reaction tank; A method of producing a carboxylic acid-terminated polyamide prepolymer by carrying out a pressurized reaction at high temperature in the presence or absence of water, and then proceeding with polymerization under normal pressure or reduced pressure, and (c) the above (a), (b), (c)
A known method can be used, such as simultaneously charging the compounds into a reaction tank, melting and mixing them, and then proceeding with polymerization all at once under high vacuum. The polyglutarimide (B) used in the present invention is a polymer or copolymer containing a cyclic imide unit represented by the following formula (). However, R ₁ , R ₂ and R ₃ in the formula each represent hydrogen or a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms. Any polyglutarimide having any chemical structure can be applied to the present invention as long as it contains the above cyclic imide unit, but usually R ₁ and
Those in which R ₂ is hydrogen or a methyl group and R ₃ is hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group are generally used.
The method for producing polyglutarimide is not particularly limited, but for example, polymethyl methacrylate described in JP-A-52-63989 is reacted with ammonia or a primary amine such as methylamine or ethylamine in an extruder. Methods that form glutarimide rings are useful. The blending ratio of the resin composition of the present invention is 5 to 80% by weight of (A) polyether ester amide, particularly preferably 10% by weight.
(B) Polyglutarimide 95-20 for ~60% by weight
% by weight, particularly preferably from 90 to 40% by weight. (A)
If the polyether ester amide content is less than 5% by weight, the antistatic properties and impact strength of the resin composition will be insufficient, and the
If it exceeds % by weight, the resin composition becomes flexible and its mechanical properties are deteriorated, which is not preferable. There are no particular restrictions on the method for producing the resin composition of the present invention, but usually (A) polyether ester amide and (B) polyglutarimide are premixed by an appropriate method, and then melt-kneaded using an extruder. It can be produced by pelletizing. The resin composition of the present invention further includes a styrene-acrylonitrile copolymer (SAN resin), a styrene-methyl methacrylate-acrylonitrile copolymer,
α-methylstyrene-acrylonitrile copolymer, α-methylstyrene-methyl methacrylate
Acrylonitrile copolymer, α-methylstyrene-styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin),
Various thermoplastic resins can be added to improve the performance as molding resins, such as methyl methacrylate-butadiene-styrene copolymer (MBS resin), polyamide, polybutylene terephthalate, and polyethylene terephthalate. It is also possible to further improve antistatic properties by adding antistatic agents such as anionic and cationic surfactants, and if necessary, various stabilizing agents such as antioxidants and ultraviolet absorbers can be added. agents, pigments, dyes,
It is also possible to add lubricants, plasticizers, etc. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The measurement of specific volume resistivity is as follows:
Using an injection molded square plate with a thickness of 3 mm, at a room temperature of 23℃,
Measured under a humidity 50% RH atmosphere. A super insulation resistance meter SM-10 manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement. Tensile breaking strength is ASTM D638, flexural modulus is ASTM D790, and Izot impact strength is ASTM
Measured according to D256. Parts and percentages refer to parts and percentages by weight. Reference Example (1) (A) Preparation of polyether ester amide A-1: Nylon 6.6 salt (AH
Salt), 72.4 parts of polyethylene glycol with a number average molecular weight of 600, and 17.6 parts of adipic acid were added together with 0.2 parts of "Irganox" 1098 (antioxidant) and 0.05 parts of tetrabutyl titanate catalyst in a reaction vessel equipped with a helical ribbon stirring blade. Prepared, replaced with nitrogen, heated and stirred at 240℃ for 40 minutes to make a transparent homogeneous solution, and then heated to 260℃ and 0.5mm.
Polymerization was carried out for 6 hours under conditions of Hg or less to obtain a viscous, colorless and transparent molten polymer. The polymer is discharged onto the cooling belt,
By petalizing, pelletized polyether ester amide (A-
1) was prepared. A-2: 20 parts of nylon 6.6 salt (AH salt), polyethylene glycol with a number average molecular weight of 1000
Using 69.8 parts and 10.2 parts of adipic acid,
Except that the polymerization time was 4 hours (A-
Polyether ester amide (A-2) was prepared in exactly the same manner as in 1). A-3: Polyether ester was produced in the same manner as in (A-1) except that 30 parts of ω-aminododecanoic acid, 19.4 parts of dodecanedioic acid and 50.6 parts of polyethylene glycol with a number average molecular weight of 600 were used and the polymerization time was 5 hours. Amide (A-3) was prepared. (2) (B) Preparation of polyglutarimide Pellets of polymethyl methacrylate were charged into an extruder together with ammonia or methylamine, and while degassing the generated gas from the exhaust port attached to the extruder, the resin temperature was raised to 280°C. Two types of polyglutarimide, B-1 (when the imidizing agent is ammonia) and B-2, are extruded with
(When the imidizing agent is methylamine) was prepared. (3) (C) Preparation of thermoplastic polymer The following polymer (C
-1 to C-3) were prepared. C-1: A thermoplastic polymer (C-1) was prepared by polymerizing methyl methacrylate. C-2: A thermoplastic polymer (C-2) was prepared by copolymerizing 70 parts of styrene and 30 parts of acrylonitrile. C-3: Acrylonitrile/butanediene = 10/
70 parts of styrene in the presence of 60 parts of copolymer rubber (NBR) with a composition of 90 (by weight)
% and 30% acrylonitrile were polymerized to prepare a graft copolymer (C-3). Example 1 The (A) polyether ester amide and (B) polyglutarimide prepared in Reference Example were mixed at the compounding ratio shown in Table 1, and the mixture was heated to a resin temperature of 230 mm using a vented 40 mmφ extruder.
Pellets were produced by melt-kneading and extrusion at °C. Next, a test piece was molded using an injection molding machine at a cylinder temperature of 230°C and a mold temperature of 50°C.
Each physical property was measured. The volume resistivity was measured under the following two conditions using an injection molded square plate with a thickness of 3 mm. (1) Immediately after molding, use detergent Mama Lemon (Lion Yushi Co., Ltd.)
After cleaning with an aqueous solution (manufactured by Manufacturer Co., Ltd.) and thoroughly cleaning with distilled water to remove surface moisture,
The humidity was adjusted for 24 hours and measured. (2) After molding, leave at 50% RH for 200 days at 23°C, wash with detergent Mama Lemon aqueous solution, then thoroughly wash with distilled water to remove surface moisture, then leave at 50% RH, The humidity was adjusted at 23°C for 24 hours and measured. The measurement results are shown in Table 1. (No. 1 to No. 8) Comparative Example The (A) polyether ester amide and (B) polyglutarimide or (C) thermoplastic polymer prepared in the reference example were mixed at the blending ratio shown in Table 1, Each physical property was measured in the same manner as in Example 1. Also (A) polyether ester amide, (B) polyglutarimide and
(C) The physical properties of the thermoplastic polymer alone were also measured in the same manner.
The results are also shown in Table 1. (No. 9 to No. 20) Example 2 In addition to (A) polyether ester amide and (B) polyglutarimide, another (C) thermoplastic polymer was blended, and the physical properties of the composition were examined as an example. Measurement was carried out in the same manner as in 1. The blending ratio and measurement results are shown in Table 1.

[Table] From the results in Table 1, the following is clear. The resin compositions (No. 1 to No. 8) of the present invention all have excellent mechanical properties represented by tensile strength at break, flexural modulus, and impact strength, and low specific volume resistivity. There is. Moreover, its resistivity hardly changes even with surface cleaning or changes over time, and it exhibits excellent permanent antistatic properties. That is, the resin composition of the present invention has both excellent mechanical properties and permanent antistatic properties. On the other hand, (A) polyether ester amide alone (No.
14-16) or (A) polyether ester amide
When it exceeds 80% by weight (No. 10), the tensile strength at break and the flexural modulus are inferior. When (B) polyglutarimide alone (No. 17, 18) or (A) polyether ester amide is contained in an amount less than 5% by weight (No. 9), the impact strength and antistatic property are insufficient. In addition, ordinary thermoplastic resins such as polymethyl methacrylate (No. 19) and SAN resin (No. 20) have high resistivity and poor antistatic properties. Further, by further mixing other (C) thermoplastic polymers to the resin composition of the present invention consisting of (A) polyether ester amide and (B) polyglutarimide (No. 21 to No. 26 ), it is also possible to obtain an antistatic resin composition with excellent mechanical properties. As explained above, the resin composition of the present invention is an antistatic resin composition that has permanent antistatic properties and excellent mechanical properties, and is expected to be used in various fields in the future.

Claims (1)

[Claims] 1 (A) (a) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of diamine and dicarboxylic acid having 6 or more carbon atoms, (b) Number average molecular weight 200 or more
5-80% by weight of polyether ester amide composed of 6000 poly(alkylene oxide) glycol and (c) dicarboxylic acid having 4 to 20 carbon atoms.
and (B) an antistatic resin composition formed by mixing 95 to 20% by weight of polyglutarimide (B).